Alkyl resin containing an oligomer mixture of unsaturated long chain fatty acids

ABSTRACT

This invention relates to an alkyd resin comprising the esterification reaction product of certain aromatic dicarboxylic acids, certain aromatic tricarboxylic acids and an oligomer mixture of unsaturated long chain fatty acids esterified with at least one hindered diol free of any carboxyl groups with or without a hindered diol compound containing a tertiary carboxyl group and/or at least one unhindered diol or at least one polyhydric alcohol having at least 3 alcoholic hydroxy groups.

i United States Patent 1191' Layman [4 July 8; 1975 1541 ALKYL -RESIN cours'mmcjauif; I 3,498,940 13/1970 Laganis.' 260/22 0 1 QLIGOM R MI 1 l3,'$3O,O82 9/l970; O'Gormanct al. 260/22 D LONG (MAIN 3,614,727 7/l972' Feketeet a1.) 260/22 D 3,719,621 3/1973 Layman. 2150/22 1) [75] Inventor: Ralph Earl Layman, S tamford;' ,w I 3,763,064. 10/1973 Soliday 260/22 D 1, ':R2 7,2 7 9 1/1972" Layman 260/22 D [-73] Assignee: A'rnerican Ciaharnid'Compan yJ T R PUBLICATIONS Stamford, Conn. 7 Boylan, Dirnerized Acids and Their use in Coil Coatings, Presented at the North Dakota State University [22] P" 1974 vEighth Annual Symposium on New Coatings and New [21] Appl No. :'$03,2l 8 Coatings-Raw Materialss M ay 30, 1966', pp. 1-26. 3"??? P-a rimary::xminr+1zpna1dw. Griffin [63] fgoyg nautagodngfiartof Ser. No. 409,223, OcL124, v Attorney? Fi J T- Dunn s21 11.5. CI...'.., 26022: 1); 1 17/132 BF; 117 132 B; 7 ABSTBACT a 1 17/161 K; 260/21; 260/22 CQ;-260/29.2'E T .'"1"! E-F?"- T', [51] Int Ch Cwd 3/64iC09d5/02 esterlfioation reactlonpro duot of certain aromatic d1- [58] new 260,22 D carboxylic'facids, certain aromatic tricarboxylic acids Y and anloligornermixture of unsaturated long chain 56] Ref-6mm cued fatty acids este'rifie'd with atleast Tone hindered diol freeof any oarb'jdxyl groups wither without a hindered AT I diol compound containing "a tertiary carboxyl group 3,158,584 I I Layman ..I.'... 260,22 D at one: or at least one g j yhydficalcohol'havingatfleast' '3 alcoholic hydroxy 3,367I894 ,2/1'968/ Bruggeman 2150/2215 gmups' 3.383.343 5/1968 Mohajer et al; 2 60/22 D 10 Claims, No Drawings 'ALKYL RESINCONTA'INING AN OLIGOMER v rxruar: or UNS'ATURATED'LONG CHAIN FATTY cres CROSSREFERENCE-TORELATEQ ArPL c rloNs f 'aackoao'uno or THE invention Alkydresins have been prepared and manufactured This application is a,c o ntinuation-in-part.of my ear H pplicationSer. No..409,223 filed Oct.-'.24 ,",.l97 3, b. nd ned; A

and sold for a plurality. of years. These alkyd resins... sometimes referred'toas polyester resins. are preparedby reacting a polycarboxylicacidwith a polyhy dric alcohol with or without an oil modifiersuch as the glyceride oils orxthe fatty acidsderivd'therefroht. More particularly these alkyd resins are generally-prepared by reacting a phthalic acid and apolyhyd ricalcohoI with orwithout additional-modifiers and the ultimate alkyd resin is useful primarily in coating compositions wherein an organicsolvent is usedasthesolvent mediumrThese improved alkyd resins display improved properties in flexibility, toughness and elasticity. Certain of these alkyd resins display good emulsion characteristics and can be dispersed in water to form anoil in water emulsion.

FIELD or rnemvenrlon DESCRIPTION OF THE PRIOR ART The references with which the instant applicant is familiar which are deemed to be themost closely related art are his U.S. Letter Pat. No. 3,158,584 and the reissue. of said patent, namely RE No. 27.279, and his U.S. Pat. No. 3,7l9,620. The instant applicant is also aware of the U.S. Pat. No. 3,235,520 'and the U.S. Pat. No. 3.530.082. All ofthese U.S. patents are incorporated herein by reference. I

SUMMARY OF THE INVENTION This invention relates to an alkyd resin comprising the esterification reaction product of (a) a mixture of (I) from about 40 percent to about 82 percent of at least one aromatic dicarboxylic acid; (2) fromabout 5 to 20 percent of at least one aromatic tri'carboxylic acid; (3) from about to percent of an oligomer mixture of unsaturated long chain fatty acid; and (4) from about 0 to 20 percent of at least one aliphatic dicarboxylic acid, wherein said percentages of acids are by weight and are based on the total weight of said ac'ids used and the total percentages amount to 100 percent. and (b) a mixture of I) from about 90 to 50 percent of at least one hindered diol free of any carboxyl groups; (2) from about 0% to ofat least one and"whichpolyhydric alcohol maybe hindered or unhindered, w'hereinlsaidpercentages of diols and polyhy- .dric 'alcohols'are percentagesjby weight based on the --.total' we ight of the alcohol component used and total I 100 percent. r ln'the'fpreparation ofthe alkyd'resin compositions oi the present invention, one will make use of at least one aromaticdicarboxylic acid of which the principal ones known-are ,in the phthallc 'acid family. Among the phthalic acids which maybe used in the practice of the processof the presentinvention arezphthaiic acid per seiisophthalic acid; terephthalic acid; endomethylene tetrahydrophthalic acid; fnaphthalic acid 1.4; naphthalic. acid l,8;l.naphthalene 1,2-dicarboxylic acid;

naphthalene-2,3 Idicarboxylic acid, naphthalic anhydride l ,8; and the halo substituted phthalic'acids such as hexachlorophthalic acid and the like. Wherever availablef'the anhydrides of these acids may be used.

These acids and/or their anhydrides may be used either singly or in combination with one another. The amount of thearomatic dicarboxylic acid or acids or mixture of acids and/or anhydrides which may be used in the formulation-of thealkyd resins of the present invention may. be varied between about percent to about 82 percent, by weight, based on the total weight of the acidcomponents used in .the alkyd resinformulation. It is preferred to use between about 55 percent and 70 percent, by weight, of the aromatic dicarboxylic acid same basis. Among the aromatic dicarboxylic acids used in the formulation of the alkyd resins of the present invention, isophthalic acid is preferred.

The second essential ingredient used in the composition of the present invention isan aromatic tricarboxylic acid. Among the aromatic tricarboxylic acids which may be used in the formulations of the alkyd resins of the present invention are hemimellitic acid, (benzene tricarboxylic acid l,2,3); trimellitic acid, (benzene tricarboxylic acid 1,2,4); trimesic acid (benzene tricarboxylic acid 1,3,5) naphthalene tricarboxylic acid l,2,3; naphthalene tricarboxylic acid 1,2,4; naphthalene tricarboxylic acid l,4,5; and the like. Wherever available the anhydrides of these aromatic tricarboxylic acids may be used and are preferred. These acids and- /or their anhydrides may be used either singly or in combination with one another. The amount of the aromatic tricarboxylic acid used in the alkyd resins of the present invention may be varied between about 5 percentto about 20 percent, by weight, based on the total weight of .the acids used in the formulation. It is preferred to use between 7 percent and l2 percent, by weight, of the aromatic tricarboxylic acid, same basis.

The third essential component used in the composition of the present invention is an oligomer mixture of unsaturated long chain fatty acids. These oligomer mixtures may contain one or more dimers of an unsaturated aliphatic monocarboxylic acid having between about l4 and 22 carbon atoms. These dimer acid compositions or mixtures are well known in the art and a plurality of these dimer compositions are available commercially. It will be apparent that these dimer acids compositions are predominately polycarboxylic acids. These dimer acids are derived by conventional procedures by dimerizing such aliphatic monocarboxylic acids as :myrisltole'ic,'palmitole'ic, oleic, linoelic, linolenic, elaeosteric, licanic, erucic, and the like. in addition onecan use asignificant amount of fatty acids in the form of blends or'mixtures of complex polymers'(oligotrimer and about 1 percentofmonomer. i-However, other lessrefined mixtures are" also very useful suchlas those containing 46'percenttrimer, 28 percemjt n mer, 11.5 percent dimer and 13.5 percent monomer.

total weight of the'alcohol component used inthepreparation of the alkydresin of the present'invention'. It is preferred to use the hindered diols free of any carboxyl group inamount varyingbetween about 65 percent and The hindered diols/containing a tertiary carboxyl grouplmayj -"be any one of-thefollowing compounds: 2,2 b is(hydroxymethyl) propionic acid, 2,2 bis(hydroxymethyllibutyrief acid; 2',2 bis(hydroxymethyl) npentanoicf,- 2,2-bis(hydroxyrnethyl). n-hexanoic acid; 2,'2 -bis'(hydroxymethyl). n-heptanoic acid; 2,2-bis(hy- 1 droxymethyl) n-octanoic acid; 2,2 bis(hydroxymethyl) Anothersuitable mixture isone containing 80% trimer andlthe balance largely dimer with a trace ofm onomer. The principal virtues of the high dimer content mixtures are better colori and'lower viscosity." Another oligomer; composition thatj is available commercially contains about;70 percent of trimer acid, about: 1 3 "per-l" cent dimer acid and about-1T percenfmon'om'erlacid, by weightflwherein saidoligomers'are derivedfrom talloil fattyffacids which are primarily oleic and linoleic' n-pelargonic- "acid, 2,2-bis(hydroxymethyl) n-capric acid and th'elike. These hindered diols may be used either 's'in glyor in combination'with one another. These hindered diols containing a tertiary carboxyl group may be (immanent the formulation altogether or may be acids. The amount of the oligomer'rnixture of the unsaturated long chain fatty acids whichmay be'used-in the formulations of the alkyd resins of the present;in-

vention may be-an amount varying between about 10 percent to about percent, by weight, based on the total weight of ,the*acids used in the formulation; lt isv preferred to use betweenabout 12 percent and l7 'percent, by weight, of the oligomer mixture, same basis.

The fourth component in the specific mixture is not an essential reactant but is preferablyused andis identified as an aliphatic 'dicarboxylic acid and preferably an aliphatic dicarboxylicacid free of any a-fl-ethylenic .unsaturation.Since this component can beleft out, one

may use none of the aliphatic dicarboxylic acid On the other hand, one may use up to about'20 percent, by weight, of this'aliphatic'dicarboxylic acid based on the total weight of the acids used. Whether there are 3'different specific components or 4, the total percentages by weightof the acids used will be 100 percent. Among the simple aliphatic dicarboxylic acids which maybe used are adipic, succinic, suberic, azelaic, sebacic, glutaric, malic, malonic, pim'elic, tartaric, and the like.

' Wherever available the anhydrides of these acids may be used. These acids and/or their anhydrides may be used either singly or in combination with one another. The preferred amount of these aliphatic dicarboxylic acids whichmay be used can be varied between about 10 percent and 15 percent, by weight, same basis asabove.

As far as the alcoholic component'used in the este'rification reaction to produce the alkyd resins of the present invention, only one class is considered to be essential and that is the hindered diols free of any carboxyl groups. Among the hindered diols free of any carboxyl groups which may be used in the preparation of the alkyd resins of the present invention are neopentyl glycol, (2,2-dimethyl propane diol 1,3); 2,2- diethylpropane diol-1,3; 2-ethy1, 2-methyl propane diol-l,3; 2-ethyl, 2-butyl propane diol-1,3; 2,2-diethyl, 1,3-hexane diol; 2,2,4-trimethyl 1,3-pentane diol; and the ester diol 2,2-dimethyl-3-hydroxypropyl 2,2- dimethyl-3-hydroxypropionate, and the like. These hindered diols free of any carboxyl groups may be used either singly or in combination with one another. They may be used in an amount varying between about 90 percent to about 50 percent, by weight, based on the used in ari'amount up ,to 25 percent, by weight, based on'the total weight of the alcohols used to prepare the alkydresins ofthei present invention. It is preferred to use 'between about-7percent and 15 percent, by

weight, of the hinde'red'diol containing the tertiary carboxyl group, 'samebasis- If desired one can use additionally in the formulation a class of diols which are identified as unhindered diols. Among the unhindered diols which may be used in the v formulations of thealkyd resin of the present invention are ethylene glycol, diethyleneglycol, propyleneglycol, Di( 1,2 propylenehglycol, butane diol 1,4; butane diol 1,3; butane diol 2,3; pentane'diol 1,5; hexane diol 1,6; heptane diol 1,7; octane diol 1,8; and the like. These diols may be used either singly or in combination with one another. These unhindered diols may be omitted from the formulation altogether or may be used in an amount of about 25 percent, by weight, based on the total "weight of the alcohols used to produce the alkyd resin of the present invention. It is preferred touse between about} percent and 20 percent, by weight, of these, unhindered diols, same basis.

, ln'combination with the unhindered diols referred to hereinabove, one may use polyhydric alcohols that contain at least 3 alcoholic hydroxy groups whether they are hindered or unhindered. These polyhydric alcohols can be used in complete substitution for the unhindered diols or may be used in combination with them. Among the polyhydric alcohols that fit into this category'are glycerol, trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, .adonitol, 1,2,6 hexane trio] and the like. These polyhydric alcohols, whether hindered or unhindered, may be used either singly or in combination with one another or maybe used in combination with the hindered diols that contain the tertiary carboxyl group. These polyhydric alcohols may be omitted completely from the formulation or-they may be used in amounts up to about 25 percent, by weight, based on the total weight 'of the alcohols used. It is preferred to use between about 8% and 20 percent, by weight, of the polyhydric alcohols that are either hindered or unhindered, same basis.

it should be noted that the maximum amount of the hindered diols free of any carboxyl groups which are mandatorily used in the composition of the present in vention is about by weight, based on the total weigh't'"of"the alcohols used. The.hindered diols containing the tertiary carboxyl group or the unhindered diols or the polyhydric alcohols containing at least three alcoholic hydroxy groupsmust make up that. ad

ditional minimum of: 10% of dio lsionpolyhyd'ric alcohols otherthanthe hindered diols that are free of any carboxylgroupsf As a consequence, a hindered diol containing a tertiary carboxyl group must be present in g H Y i "se d onthetotal,

- weightof the alcohols'usedif.therel rs noiun hi ndered diol and fno'polyhydric alcoh'olfusedl On' thej other} hand; if there is'used no hindered diol a I an amou'nt'of at least'1l07c. by weight b tiar y carboxyl group then. one must use at least '1 dip er i cent, by weight. based 'on the total we i gh t of thealco:

hols used of at least one unhindered diolor l percent. by weight. of at least one polyhydric alcohol having at least 3 alcoholic hydroxyl groups. As a consequence, whateveris contained in' the mixture of'those m pounds containing alcoholic hydroxyl groups one must have a total of ,lOO. percent of the various components .in the mixture.- When one usesonlySO percentpby weight. of at least onehindereddiol free from any carboxyl groups. onemust then use at least l5 percent,by weight, of at least one hindered diol containing a tertiary carboxyl group and at least'S percent, by weight,

prior to the addition of the mixture of oligomer of the unsaturated long chain fatty acids. Alternatively, one may introduce the oligomer mixture and the polyhydric alcohol composition and esterify these reactants in part with one another prior to the addition of the aromatic dicarboxylic acid component. Still further, one may introduce all of the acidic components (except the tricarboxylic aromatic acid) and the polyhydric alcohol com ponents into the reaction vessel, namely the aromatic dicarboxylic acid. the mixture of oligomer with or without any aliphatic dicarboxylic acid together with the hindered diol free of any carboxyl groups, with or without the hindered diol containing a tertiary carboxyl group, with or without an unhindered diol or a polyhydric alcohol having at least 3 alcohol hydroxy groups and carryout the esterification reaction by heating the mixture with substantially constant agitation or stirring 'until an acid number of about 20 has been reached.

The aromatic tricarboxylic acid is then added. The reaction should be continued until the esterification has proceeded sufficiently to produce a composition having an acid number of at least 20 and preferably at least 40 although acid numbers as high as 70-80 are useful. The preferred range of the acid number is between about 40 and 60. The acid number of this alkyd resin is derived from 3 sources l) the unreacted carboxyls of the dicarboxylic acids, mainly the phthalic or isophthalic acid employed. (2) the tertiary carboxyl on the hindered glycol suchas the 2.2-bis(hydroxymethyl)propionic acid and (3) largely from the aromatic tricurboxylic acid such as the trimellitic anhydride. This latter material is generally added to the polyester I in preparing the alkyd resins of theipresentinventior one may use stoichiometrically calculated amounts of the hydroxyl and carboxyl components. Alternatively one may use an excess, of the hydroxyl component amounting to. as much as percent over and beyond thestoiehiometrically:calculated amounts of the hydroxylcomponent required to esterify completely the calculatedcarboxylcom ponent. It is preferred to use .about5 percentitoabout;lO'percent-excess of the hyldroxylcomponent,over the carboxyl component on a stoichiometrically calculated basis. For certain purposes, particularly where water dispersible alkyd resins are required. it may be desirable to use an excess of the carboxyl componentsarnounting toas much as 25 percent in excess of the,hydroxyl-component, again on a stoichiometrically calculated'basis-.-As before, it is pre' ferre diin certain instances. to use about 5 percent to about 15- percent excess of the carboxyl component over the hydroxyl component on a stoichiometrically calculated basis.

The alkyd resins of the present invention are compositions of reacted materials which have been chemically resin or alkyd resin just a short time before the end of i groups.

reacted together to produce a resinous alkyd that is suitable for preparing industrial baking enamels. When organic orinorganic bases are added to the alkyd resin. it may be thinned with water. Esters and particularly polyesters in the presence of water sometimes have had a tendency to hydrolize back to, the initial starting components. This hydrolysis is promoted by heat, high and low pH and byother catalytical materialssPaints which sis cannot be totally prevented, hindered polyols alone are not the complete answer. I have discovered that a hindered glycol containing a tertiary carboxyl group improves further the stability of the alkyd resin in water. The exact mechanism by which this improvement is effected is not completely known but it may be speculated that it affords an anionic or solubilizing group to a molecular chain irrespective of whether the chain is terminated by a hydroxyl group, a carboxyl group or an alkyl group.

Since the alkyd resins of this invention are soluble in organicwaterimmiscible solvents as well as water miscible organic solvents, the stability therein is also important for those applications which will first dissolve the polyester in said solvents. For example an equal part mixture of n butanol and butoxy ethanol is a suitable solvent that is water miscible. it has been discovered that if the hindered diol free of any carboxyl group is present in the reaction mixture in a content of a polyol which exceeds about percent of the total polyol content of the polyester. then the solution becomes cloudy due to crystallization. The balance of the polyol is. therefore, to be made up from a hindered diol containing a tertiary carboxyl group such as the 2,2- bis(hydroxymethyl)propionic acid totally or at least 50 percent of the balance of the polyol used. Because of the several ways in which a polyester resin may manifest instability, the relative amounts of the various components happens to be limited.

, I 3,893,959 in '11 The alkyd resins of the present invention make excelfered. on an automotive body partQsuch as a fender. the lent coatingr esinswhichmay be used preferably in same could be hammeredout to1substantiallyoriginal combination with-aminoplast resins which will be dis-, form without need'forfa'recoating except possibly in excussed inL greater detail hereinbelow or with nitrocellu-f'. treme ca ses when thedamage was so. great as to render lose lacquers.*Whenusedwitnaminoplastresins;the "5 jsuchah approachnot pc ssible: "1'? I 2i", novel alkyd resins ofthepresent invention may be can; The aminoplastnsins usedfwiththe alkydresin's of with an 'appropriatesolvent-suchfasinert organicsbl I vent. Amongthe' inert organic-solvents;which may be? termused to"identify' them.Among the aminoplast resused as asolvent mediumKfQr'th'e novel 'resinsfof the inswhich may.beutilizedincombination with the novel present invention are benienejtoluene. xylene or Sol-{lid alkyd resins of the present invention are thoseresinous {the pre'sent'invention are well known in the art as is the vesso No. l00 or NofjlSO, butanol, methylisobu- If. materialsprepared b'y reacting-an aldehyde'such as fortylketone, butyl acetate and the like. The amount of the v maldehyde with a compound such as 'urea,thiourea,' disolvent utilized with thenovel resins of the present ln-- ii cyandiamide or the timonotriazines such as melamine, vcntionis not critical and proportions conventionally benzogua'namine acetoguanamlne, formoguanamine, used inthe art may be observed depending ontheulti and the "like.- -The mo lratios of the aldehyde to the mate mode of use offthecoating" composition fofjith aminqea pouham allwellknown in thegart dependpresent invention-T h compos'itions may s appii ing-ionflthe irpa'riticularamineflsele'ctedand it lis not by brushing, roller coating," spraying, knife coating-hot I deemed necessary therefore to elaborate further on demelt and the likeQFor-certainapplications, no dilutingf tails"that arel j-well' knownin the 'artLf These aminesolvent medium is necessary suchas in the case of hot'-; j aldehyderesins or" potentially resin ffor'ming materials meltadhe'sives. Quite obviously, if one wants a clear 5 may b'e'alkylated or 'unalkylated' The alkylate'daminocoating, no additives'suchas dyes andpigments 'willbe plast-resins are those which have'been reacted with a added. On the other hand,if'one wishes'a colored'coat .monohydric aliphaticalcohol such'las methanol, ethaing composition, the'selecteddy'e and/or pigmentfrn ay "nol, propanol, butanol and the like. The degree of alkybe added according' to choice in conventionalquantilation may also be varied significantly as is wellknown ties. in the art and furtherelaboration of this'conceptis also in the preparation of the alkyd resins of the present deemed to be unnecessary. The preferred aminoplast invention, onewould heat the reactants to an "elevated materials used inthe composition of the present inventemperature such as between about l90C. and 250C. tion are the polymethyl ethers of polymethylol meluntil the desired'acid number has been reached as disamines includingthe dimethyl ether of dimethylol'melcussed 'hereinabove. Preferably one'would utilize temamine, tetrameth'yl ether of tetrame'thylol melamine peraturesv-arying between about 215C. and 235 C. and particularly' preferred fisthe hexamethyl ether of The alkyd resins of the present invention,jwhen hexamethylolmelamine. it should be-noted'that these blended with aminoplastresins in certain proportions,f polymethyl ethers of 'polymethylol melamine may be produce coating compositions which are capableof resinous or nonresinous as used in the coating composiproducing films that possess a combinationofproper tions of the rpresentiinvention. )lf j'thesemat'erials are ties not previously known in most coating composinonresinous"no-significant condensation has 'taken tions. These outstanding properties are to be noted parplace and therefore these materials arein a sense monticularly in the area of impact resistance and hardness. omeric in form-.butiare unquestionably potentially resin The impact resistance of the films'rproduced'by the forming'material's ;"i.e'., thesematerials are capable of blend of the alkyd resins of the present invention with being converted into resinous'materials upon use'such aminoplast resins or resin forming compositions, par as heat, i .e.,baking.The amount of aminoplast material ticulariy the polymethyl ethersof polymethylol mel-. used in the composition of thepresent invention may amines, is so surprisingly excellent that it is possible bevaried to some extent but not over a very substantial through the use of this novel-coating composition to range. The amount of aminoplast material should be coat sheet steel with these coatings and upon drying, limited withinthe range of about 5 to percent, by such as by baking, the coated steel sheet can then be weight, based on'the total weight of aminoplast matefabricated into, many desired contours without any disrial and alkyd resin. preferably, the aminoplast material play of crackingor peeling which would normally be 50 should be varied between aboutiS percent and 25 perexperienccd even with other conventional commercent, by weight,-based on the-total weight of the aminocially available alkyd coating compositions currently plast material and-thealkyd resin; The compositions of on the market. This outstandingly advantageous prop- ,the' present invention can bs'moainearunher by the erty wouldpermit (l) the coating. of metal sheets such addition Ito theHalkyd,resin arninoplast composition, as sheet steel to be utilized in the, manufacture of varying proportions of. nitrocellulos lacquers, epoxy household appliances such as refrigerators, stoves, resins, polyvinyl chloride resins and the like.

washing machines and the likeand (2) thevpostforming ln orderthat the concept of the present invention of the coated sheet to the desired shapeand configuramay be morecompletely understood, the following extion. Still further, the coating compositions of the pres-' amples are set forth in which all parts are parts by ent invention could be utilized in metal sheets that are weight unless otherwise indicated. These examples are to be fabricated into automotive body parts such as set forth primarily for. the purpose of illustration and fenders, hoods and the like. Additionally,-a further adany specific enumeration of detail contained therein vantage associated with the compositions of the present should be interpreted as a limitation on the case except invention resides in the fact that an automotive body as is indicated in the appended claims.

part, coated with the alkydaminoresin composition of the present invention could experience accidental EXAMPLE i denting without displaying cracking or peeling of.the into a suitable reaction vessel equipped with an agitacoating on the metal. When such a dent were to be suftor, thermometer, inert gas inlet tube, and partial con- SKparts of trimethylol propane. 74 parts of dimethylol propionic acid,f303 parts of adipic acid. 240 partsofa mixture of oligomerscontaining about 70fpercen'tfof trimer acid. about'l3 percent dimer acid'and about-17' 'acid and 265 parts onhe same mixture percent monomer acid. by weight. wherein said oligomers are derived from tall oil fatty. acids which are primarily oleic and linoleic acids and "1087 parts ofisophthalic acid. These reactants are heated under a'blan ket-of'nitrogen'to a reaction temperature of about l 65 l90 C.-while thewater of esteriiication is continuously removed with constantagitation. The heating'is -theniincreased and the temperature slowly"rises to about230C. as the isophthalic acid reacts.When the reaction mass is clear. the acid number is about-20-25,

the temperature is quickly lowered to about 190C. and 64 grams oftrimellitic anhydride are added. After holdingthe reaction mass for an additional 30 minutes at 185C.'the acid number is 44. The resin is then poured into a pot and cut to 75 percent resin'solids content using n-butanol and n-butoxy ethanol.

EXAMPLE 2 :Example 1 is repeated in all essential details except that the amount of neopentyl glycol used is 866 parts and dipropylene glycol amounting to 74 parts is used to.

EXAMPLE 3 lnto a suitable reaction vessel equipped as in Example 1 there is introduced 910 parts of neopentyl glycol, 59 parts of trimethylol propane, 87 parts of dimethylol propionic acid, 1,038 parts ofisophthalic acid, 330 parts of adipic acid and 240 parts of the same mixture of oligomers of unsaturated long chain fatty acids used in Example 1. The reactants are heated as in Example 1 until an acid number of 25 is reached, whereupon the resin is then cooled to about,f-90C. and 102 parts of trimellitic anhydride are added. After one additional hour at 185C. the resin has an acid number of 43. The resin is cooled, to about 160C. and is cut with a mixture of equal parts of n-butanol and n-butoxy ethanol to a resin solids content of about 75 percent.

The oligomer composition used in Examples 1 to 5 is principally a trimer acid composition comprising polymers of unsaturated aliphatic monocarboxylic acids having between 14 and 22 carbon atoms derivedfrom tall oil fatty acids which are primarily oleic and linoleic acid. These acid compositions are known in the art and are commercially available. The trimer acid per se in the trimer acid composition is present in prepondent amounts such as about 70 percent, by weight, while the dimer content is about 13 percent and about 17 percent monomeric acid wherein the percentages total 100 percent. By using a mixture of commercial products. a great variety of compositions is possible.

l0 COMPARATIVE EXAMPLE 4 lnto a suitable reaction yessel equipped as in Exam ple 1. there is introduced 763 parts of propylene glycol 72' parts of .trimethylol propane, 1,180 parts of iso .oligomers'of fatt'ylacids as was used in Example 1. Tht

-'charge.is heated gradually to 235C. under a blanket o nitrogen gas. When an acid n umber of 20 is reached thereaction vessel contents-are cooled to abou 2 00 C.-,' Twher eupon 331; parts of adipic acid are added Thetem'p erature is held at 2009C. until an acid numbe of 42 to 45 is reached. Thetemperature is then reduce to 160C. and the resin is then cut with butoxy ethano and n-but anol to a solids content of 75 percent. Th viscosity,jon'the Gardner-Holdt scale at C. is Z u .2

EXAMPLE 5 2O lnto a suitable reaction vessel equipped as in Exam plel thereis introduced 930 parts of neopentyl glycol 105 parts of trimethylol propane, 330 parts of adipic acid,.240 parts of the same mixture of oligomers 0: fatty acids as wasused in Example 1, 1,040 parts of iso 5 phthalic'acid 'and'102 parts of trimellitic anhydride These materials are processed to a resin accoiding tc theprocess set forth in Example 1, except that the final acid number is 40. When cut to a 75 percent solids solution by the use of equal weights of butoxy ethanol and n-butanol, the viscosity on the Gardner-holdt scale at 25C. is Z,.

COMPARATIVE EXAMPLE 6 I I u u lnto a suitable reaction vessel equipped as in Exampie 1, there is introduced 517 parts of 1,2-propylene glycol, 97 parts of trimethylol propane and 696 parts of is'ophthalic acid. The charge is heated in the manner of Example 1, until an acid numberof 25 is reached. The temperature is reduced from 220C. to 175C. and 438 parts of adipic acid are added. The temperature is raised to 190C. in order to react the'adipic acid. After 2 hours, when theacid number is 44, the temperature is reduced to 155C. and the resin is cut to a 75 percent solids solution by using a 50/50 mixture of butoxy ethanol and n-butanol. The viscosity on the Gardner-Holdt scale at 25C. is Z, to Z Baking enamels are prepared from the resins of Examples 1 to 6, inclusive, by adding to each of these resins a sufficient amount of hexakis (methoxymethyl) melamine so as to provide an 80/20, alkyd/melamine compound ratio on a solids basis. Titanitim dioxide is next dispersed into each mixture using a ratio of 80/100, pigments/resin ratio, on a solids basis. The catalyst system, p-toluene sulfonic acid, is added as a 20 percent alcoholic solution, in an amount sufficient to provide 1 percent of catalyst by weight based on the total resin solids. Each enamel is then thinned to a 43% total solids solution, using water and dimethylethanolamine such that the final pH is 8.5. Films having a thickness of 3 mils are drawn down on chromate treated steel and the panels are baked for 20 minutes at 350F. The panels were examined and tested and the films yielded the results set forth in Table 1 as under:

12, Q A LE 1 Cont inued Ext. i 2 1 39: J4 i .6 Swardlla rdncss 44 f 46 -52 .42 52 36 Reverse Impact I30 l40- I401 90 140 l .80 l Adhesion, .89 4

good

good good good good -Reverse l riipnctazalues stated in inch v ,Samplesof each resin' solution were neutraliz ed; with};

dimethylethanolamine' and reduced furtherjwith water to a 40 percentsolids'solution. The'pH' wasagainfadjusted to 8.3 and these samples of e'ach resin, in closed glass jars, were stored in an oven setiat 130F. inorder to test hydrolytic stability. Frequent examinations'dis closed the time for each solution to separate into twophases. When this occurred. the pH was always below.

7 and usually at 6.6. The various examples had the fol-' lowing 130F. stabilityz" TABLE ii 4 Ex. 1 28 days Ex. 4 days Ex. 2 days Ex. 5 10 days Ex. 3 days Ex. 6 4 days Aliquots of each of the baking enamels were stored for one week in an ovenheld at l F. Upon removal from the oven, thosecoating compositions made from Examples 1, 2 3 and 5 showed only a slight fall-off in hardness, while gloss, viscosity, impact resistance and solvent resistance remained at least as good as before the oven storage. On the other hand, those enamels made from the resins of Examples 4 and 6 had separated into two phases and could not be stirred up into homogenous specimens again. The above mentioned behavior of the enamels at 130F. storage illustrates clearly the superiority of the hindered glycols toward hydrolysis.

EXQ'AMPLE 7 into a suitable reaction vessel equipped as in Example I there is introduced 540 parts of neopentylglycol, 540 parts of 2,2,4-trimethyl pentane-diol l -3, 60 parts of trimethylol propane, 87 parts of dimethylol propionic acid, 240 parts of the same mixture of oligomers of fatty acids as was used in Example l, I050 parts of isophthalic acid, and 330 parts of adipic acid.

The processing of these reactants is substantially the same as in Example l. When the acid number reaches 20-25 and the product is clear, in contrast to turbid, the resinous mass is cooled to 190C. and thereupon 100 parts of trimellitic anhydride are added. The temperature is then maintained at l85C. until the acid number reaches 45 i 2. The resin is then cooled and cut with the solvent as in Example I, yielding a viscosity of Z,-, on the Gardener-Holdt scale at 25C., and a solids'of 75 percent. This resin was made into a baking enamel as was done with the resins of Examples l-6 inclusive, and performed in all essential respects in a manner equal to Examples 1, 2 and 3.

EXAMPLE 8 l1280 'partsof.adipic acid. l,080.pa r ts is'o'phthalic acid and 280 parts of an oligomer mixture derived'from soybean oil fatty acids, having the average composition of about percent dimer acids, about 13.8 percent oftrimer acids, and about l,.2 percent of monomeric acids.

.Soybeanoil contains relatively small amounts of satu rated acids such as palmitic, stearic, and arachidic. Additionally soybean oil fatty acids contain asunsaturated .yacids about 52.5 percent of linoleic acid, about 33.5 percent ofoleic acid and about 2.3 percent oflinolenic acid. Usingthe procedure as set forth in Example 7, the heating is continued until an acid number of 22 is reached. Thereupon the resin is cooled to about 190C. and llO parts of trimellitic anhydride are added. After holding at a temperature of about l80-l85C. for 30 minutes, the resin is cooled to about 150C. and then thinned with solventasin Example l to about 75 percent solids. This resin solution is made into a baking enamel as was done inthe'Examples l-6 inclusive and the resulting baking enamel performed in all essential respects equal to the enamels of Examples l, 2 and 3.

I claim:

1. A hydrolytically stable alkyd resin which is capable of being rendered water dispersible comprising the esterification reaction product of a. a mixture of I) from about 40 to 82 percent of at least. one aromatic dicarboxylic acid; (2) from about 5% to 20 percent of at least one aromatic tricarboxylic acid; (3) from about 10 to 20 percent of an oligomer mixture of unsaturated long chain fatty a'cids; and (4) from about 0 to 20 percent of at least one aliphatic dicarbiixylic acid, wherein said percentages of acids are by weight based on the total weight of said ac'ids used and total 100 percent, and b. a mixture of I) from about to 50 percent of at least one hindered diol free of any carboxyl groups;

(2)Ifrom about 0 to 25 percent of at least one hindered diol containing atertiary carboxyl group; and (3) from about 0 to 25 percent of at least one unhindered diol or at least one polyhydric alcohol having at least three alcoholic hydroxy groups, wherein said percentages of diols and polyhydric alcohols are by weight based on the total weight of the alcohols used and total percent. 2. An alkyd resin according to claim 1 in which the s hindered diol compound containing a tertiary carboxyl group is 2,2-bis(hydroxymethyl) propionic acid.

3. An alkyd resin according to claim 2 in which the hindered diol compound free of any carboxyl groups is neopentyl glycol.

4. An alkyd resin according to claim 2 in which the aromatic dicarboxylic acid is isophthalic acid.

5. An alkyd resin according to claim 1 in which the aromatic dicarboxylic acid is isophthalic acid.

6. An alkyd resin according to claim 1 in which the hindered diol compound free of any carboxyl groups is neopentyl glycol.

7. An alkyd resin according to claim 6 in which the aromatic dicarboxylic acid is isophthalic acid.

, 13f 8. Analkyd resin accordingt o claim 1 in which the aromatic tric arboxylic acid is irimellitic acid.

9. An alkyd resin according to claim 2 in wliich the I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5 95, 959 Dated y 8 975 Inventor(s) Ralph Earl Layman It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

IN THE TITLE, delete "ALKYL" and substitute therefor ALKYD Col. 8, line 62, insert not after "should".

Col. 9, line 31, delete "Z -2 and insert therefor Z Z Signed and Sealed this A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting ()jficer (nmmissinncr of Patents and Trademarks 

1. A HYDROLYTICALLY STABLE ALKYD RESIN WHICH IS CAPABLE OF BEING RENDERED WATER DISPERSIBLE COMPRISING THE ESTERIFICATION REACTION PRODUCT OF A. A MIXTURE OF (1) FROM ABOUT 40 TO 82 PERCENT OF AT LEAST ONE AROMATIC DICABOXYLIC ACID, (2) FROM ABOUT 5% TO 20 PERCENT OF AT LEAST ONE AROMATIC TRICARBOXYLICACID, (3) FROM ABOUT 10 TO 20 PERCENT OF AN OLIGOMER MIXTURE OF UNSATURATED LOMG CHAIN FATTYB ACIDS, AND (4) FROM ABOUT 0 TO 20 PERCENT OF AT LEAST ONE ALIPHATIC DICARBOXYLIC ACID, WHEREIN SAID PERCENTAGES OF ACIDS ARE BY WEIGHT BASED ON THE TOTAL WEIGHT OF SAID ACIDS USED AND TOTAL 100 PERCENT, AND B. A MIXTURE OF (1) FROM ABOUT 90 TO 50 PERCENT OF AT LEAST ONE HINDERED DIOL FREE OF ANY CARBOXYL GROUPS, (2) FROM ABOUT
 0. TO 25 PERCENT OF AT LEAST ONE HINDERED DIOL CONTAINING A TERTIARY CARBOXYL GROUP, AND (3) FROM ABOUT 0 TO 25 PERCENT OF AT LEAST ONE UNHINDERED DIOL OR ATLEAST ONE POLYHYDRIC ALCOHOL HAVING AT LEAST THREE ALCOHOLIC HYDROXY GROUPS, WHEREIN SAID PERCENTAGES OF DIOLS AND POLYHYDRIC ALCOHOLS ARE BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE ALCOHOLS USED AND TOTAL 100 PERCENT.
 2. An alkyd resin according to claim 1 in which the hindered diol compound containing a tertiary carboxyl group is 2,2-bis(hydroxymethyl) propionic acid.
 3. An alkyd resin according to claim 2 in which the hindered diol compound free of any carboxyl groups is neopentyl glycol.
 4. An alkyd resin according to claim 2 in which the aromatic dicarboxylic acid is isophthalic acid.
 5. An alkyd resin according to claim 1 in which the aromatic dicarboxylic acid is isophthalic acid.
 6. An alkyd resin according to claim 1 in which the hindered diol compound free of any carboxyl groups is neopentyl glycol.
 7. An alkyd resin according to claim 6 in which the aromatic dicarboxylic acid is isophthalic acid.
 8. An alkyd resin according to claim 1 in which the aromatic tricarboxylic acid is trimellitic acid.
 9. An alkyd resin according to claim 2 in which the aromatic tricarboxylic acid is trimelLitic acid.
 10. An alkyd resin according to claim 3 in which the aromatic tricarboxylic acid is trimellitic acid. 